CN100417422C - Superabsorbent polymer with slow absorption times - Google Patents
Superabsorbent polymer with slow absorption times Download PDFInfo
- Publication number
- CN100417422C CN100417422C CNB2004800333606A CN200480033360A CN100417422C CN 100417422 C CN100417422 C CN 100417422C CN B2004800333606 A CNB2004800333606 A CN B2004800333606A CN 200480033360 A CN200480033360 A CN 200480033360A CN 100417422 C CN100417422 C CN 100417422C
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- Prior art keywords
- superabsorbent polymer
- polymer composition
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- weight
- polymer
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- 229920000247 superabsorbent polymer Polymers 0.000 title claims abstract description 101
- 238000010521 absorption reaction Methods 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 28
- 239000002250 absorbent Substances 0.000 claims description 22
- 239000008187 granular material Substances 0.000 claims description 18
- 230000035699 permeability Effects 0.000 claims description 17
- 239000004971 Cross linker Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000007667 floating Methods 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 230000003204 osmotic effect Effects 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
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- 239000003795 chemical substances by application Substances 0.000 abstract description 6
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
Abstract
The invention relates to hydrophilic superabsorbent polymer comprising a) from about 55 to about 99.9 wt.% of polymerizable unsaturated acid group containing monomers; b) from about 0.001 to about 5.0 wt.% of internal crosslinking agent; c) from about 0.001 to about 5.0 wt.% of surface crosslinking agent applied to the particle surface; and d) wherein the composition has a degree of neutralization of more than about 20%, and from about 20 mole % to about 75 mole % of the unsaturated acid group containing monomers are neutralized with a first neutralizing agent, and from about 5 mole % to about 40 mole % of the unsaturated acid group containing monomers are neutralized with a second neutralizing agent; at a temperature of about 75 DEG C or less. Such hydrophilic superabsorbent polymers have an Absorption Time of about 5+10 a 2 minutes or greater, where a is the mean particle size of the superabsorbent material in millimeters, a capacity of about 15 g/g or greater, a Drop Penetration Value of about 2 seconds or less, and a 1/2 Float Saturation of 50% or less.
Description
Invention field
The present invention relates to absorb the super absorbent polymer of water, liquid, aqueous and blood, described super absorbent polymer wherein of the present invention has the characteristic of improvement, has slower soak time especially, and keeps satisfied fluid retention characteristic simultaneously.The invention still further relates to the preparation of these super absorbent polymers and they are as the purposes of absorbent in hygienic articles and in industrial circle.
Background of invention
Superabsorbents is meant and can absorbs at least about 10 times of water swellable, water-fast organic or inorganic materials to own wt and about at the most 30 times of own wts in the aqueous solution that contains 0.9 weight % sodium chloride solution in water.According to the General Definition of superabsorbents, super absorbent polymer be can absorb a large amount of liquid, aqueous and body fluid such as urine or blood and swelling and formation hydrogel and can be under certain pressure with the cross linked polymer of its maintenance.
The described super absorbent polymer that can commercial obtain is cross linked polyacrylate or crosslinked starch-acrylic acid-grafted polymer at present, wherein with in sodium hydroxide solution or the potassium hydroxide solution and the part carboxyl.As the result of these characteristics, mainly these polymer are used for adding hygienic articles such as baby diaper, incontinence articles or sanitary towel.
For reason healthy, comfortable and attractive in appearance and from the environment aspect, there is the growing trend that hygienic articles is littler and thinner that makes.This can realize by the content that reduces the high power capacity villus fiber in these goods.In order in described hygienic articles, to guarantee the total reserve capability of constant body fluid, in these hygienic articles, used the super absorbent polymer of bigger content at present.Therefore, super absorbent polymer must have the Penetration Signature of raising, and keeps other characteristics such as enough absorbability and retention simultaneously.
Especially, gel blockage be possible with in absorbing products such as diaper, use the relevant known problem of super absorbent polymer.When body fluid enters the quick swelling of described superabsorbent polymer particles around the absorbing products place and when causing gap in the SAP-fine hair substrate and hole to be closed, gel blockage can take place.Since the liquid transfer by diffusing through the swelling hydrogel than the transmission of passing described gap slowly many, thereby enter in the zone at fluid sealing effect can take place.This effect is called as gel blockage.
Pass the liquid transfer of swelling superabsorbent polymer particles itself and follow diffusion law, and be process very slowly, this process is distributed the liquid in the hygienic articles user mode and is cut little ice.Can not keep owing to lack gel stability open bed formula structure with the super absorbent polymer that influence the capillary transfer effect in, guarantee the separation each other of described granule by embedding super absorbent polymer in fibre substrate.
For being known as follow-on diaper structure, in described absorber layer, there being less fibrous material or not existing fibrous material to help fluid transfer or to keep open fluid permeable structure.The described super absorbent polymer of these diaper structures of future generation must have sufficiently high stability under solvent swelling state, be commonly referred to gel strength, and therefore described swell gel has the capillary space of q.s, and liquid can pass these spaces and transmit.
In order to obtain having the super absorbent polymer of high-gel strength, can increase the degree of cross linking of described polymer, but this will inevitably cause the reduction of swellability and reserve capability.In order to obtain the permeability of raising required in having the goods of future generation as thin as a wafer of low fiber content, prior art has been instructed and the amount of covalent cross-linking can have been increased to high level, make the absorbability of described super absorbent polymer and retention be reduced to undesirable low-level on.
Found by making superabsorbents have slower swelling rate, fluid transmission and permeability can be maintained by the rapid expanding of avoiding the described superabsorbent polymer particles around body fluid enters the absorbing products place in thin, low-fiber goods of future generation, described rapid expanding can cause closing of described gap and hole in SAP-fine hair substrate, i.e. gel blockage.Therefore, can under the situation that does not rely on excessive crosslinked described super absorbent polymer, avoid gel blockage, thereby realize permeance property.Super absorbent polymer with low absorption rate known in the art is realized the swelling rate of its reduction by the coating of hydrophobic treatment or delayed absorption.Hydrophobicity is undesirable, because it can reduce the capillary transfer ability of bulk polymer and can stop that SAP's is moistening.Slowly dissolving coating (for example having gelatin) can increase described fluidic viscosity in absorbing products, because they can dissolve and hinder the fluid transmission.
Therefore, the purpose of this invention is to provide absorbent polymer composition, absorption rate by the described polymer of restriction under the situation of not introducing hydrophobicity or serviceability obstruction coating, even when the percetage by weight that increases based on the described super absorbent polymer of described absorbent structure, described compositions also can demonstrate excellent specific property as keeping the ability that high permeability for liquids, hydrophilic and liquid keep.
The invention summary
The present invention relates to the hydrophilic super absorbent polymer, it comprises a) the polymerisable undersaturated monomer that comprises acid groups of about 55～about 99.9 weight %; B) internal crosslinker of about 0.001～about 5.0 weight %; C) surface crosslinking agent that puts on particle surface of about 0.001～about 5.0 weight %; And d) wherein, described compositions has the degree of neutralization greater than about 20%, and under about 75 ℃ or lower temperature, the monomer that about 20mol%～about 75mol% described undersaturated is comprised acid groups neutralizes with second nertralizer with neutralization of first nertralizer and the described undersaturated monomer that comprises acid groups that will about 5mol%～about 40mol%.
The invention still further relates to the super absorbent polymer with following character: soak time (AbsorptionTime) is about 5+10a
2Minute or longer, wherein a is the mean diameter of described super-absorbent material in millimeter, the capacity of determining by the FAUZL test is about 15g/g or bigger, drop osmotic value (DropPenetration Value) is that about 2 seconds or shorter and 1/2 floating saturation (Float Saturation) are about 50% or littler.
The invention still further relates to super absorbent polymer, it comprises a) the polymerisable undersaturated monomer that comprises acid groups of about 55～about 99.9 weight %; B) internal crosslinker of about 0.001～about 5.0 weight %; C) surface crosslinking agent that puts on particle surface of about 0.001～about 5.0 weight %; And d) wherein, the described undersaturated monomer that comprises acid groups has the degree of neutralization greater than about 25%, and the described undersaturated monomer that comprises acid groups that will about 20mol%～about 75mol% neutralizes with second nertralizer with neutralization of first nertralizer and the described undersaturated monomer that comprises acid groups that will about 5mol%～about 40mol%; The soak time of described super absorbent polymer is about 5+10a
2Minute or longer, wherein a is the mean diameter of described super-absorbent material in millimeter, the capacity of determining by FAUZL test is about 15g/g or bigger, the drop osmotic value is that about 2 seconds or shorter and 1/2 floating saturation are about 50% or littler.
The accompanying drawing summary
Fig. 1 is the device sketch map that is used for determining overflowing under the zero load of super-absorbent material absorption (FAUZL) value.
Fig. 2 overflows the viewgraph of cross-section of the device of absorption (FAUZL) value along the part of hatching B-B under the definite zero load that is shown among Fig. 1.
Fig. 3 overflows the viewgraph of cross-section of the device of absorption (FAUZL) value along the part of hatching A-A under the definite zero load that is shown among Fig. 1.
Fig. 4 is the device sketch map that is used for gel bed permeability (GBP) value of definite super-absorbent material.
Fig. 5 is the viewgraph of cross-section along the piston head of the line 12～12 of Fig. 4.
The description of preferred implementation
The natural polymer and the material of natural, biodegradable, synthetic and modification that suitable super absorbent polymer can be selected from.The term " crosslinked " that relates to described super absorbent polymer is meant and makes the water insoluble basically but any way of swellable of normal water soluble materials effectively.Described crosslinking method comprises for example physical entanglement, crystalline state farmland, covalent bond, ion cooperation and association, hydrophilic association such as hydrogen bonding, hydrophobic association or Van der Waals force.Super absorbent polymer comprises internal crosslinking and surface-crosslinked.
An embodiment of the invention relate to hydrophilic super absorbent polymer, and it comprises a) the polymerisable undersaturated monomer that comprises acid groups of about 55～about 99.9 weight %; B) internal crosslinker of about 0.001～about 5.0 weight %; C) surface crosslinking agent that puts on particle surface of about 0.001～about 5.0 weight %; And d) wherein, described compositions has the degree of neutralization greater than about 20%, and under about 75 ℃ or lower temperature, the described undersaturated monomer that comprises acid groups of about 20mol%～about 75mol% is neutralized with first nertralizer, and the described undersaturated monomer that comprises acid groups that will about 5mol%～about 40mol% neutralizes with second nertralizer.
Another embodiment of the invention, described super absorbent polymer is a cross linked polymer, the soak time of wherein said super absorbent polymer is about 5+10a
2Minute or longer, wherein a is the mean diameter of described super-absorbent material in millimeter, liquid capacity is about 15g/g or bigger, the drop osmotic value is that about 2 seconds or shorter and 1/2 floating saturation are about 50% or littler.Preferably, described super absorbent polymer demonstrates about 20g/g or bigger FAUZL liquid capacity, and 20 * 10
-9Cm
2Or bigger gel bed permeability.A preferred implementation is that liquid capacity is that about 25～about 36g/g and gel bed permeability are about 5～92 * 10
-9Cm
2Super absorbent polymer.
In yet another embodiment of the present invention, described super absorbent polymer is a cross linked polymer, and it comprises a) the polymerisable undersaturated monomer that comprises acid groups of about 55～about 99.9 weight %; B) internal crosslinker of about 0.001～about 5.0 weight %; C) surface crosslinking agent that puts on particle surface of about 0.001～about 5.0 weight %; And d) wherein said compositions has the degree of neutralization greater than about 20%, and the described undersaturated monomer that comprises acid groups that will about 20mol%～about 75mol% neutralizes with second nertralizer with neutralization of first nertralizer and the described monomer that comprises the unsaturated acids group that will about 5mol%～about 40mol%; Its soak time is about 5+10a
2Minute or longer, wherein a is the mean diameter of described super absorbent polymer in millimeter, the capacity of determining by FAUZL test is about 15g/g or bigger, the drop osmotic value is that about 2 seconds or shorter and 1/2 floating saturation are about 50% or littler.
Obtain described super absorbent polymer of the present invention by the polymerisable undersaturated monomer initial polymerization that comprises acid groups with about 55～about 99.9 weight %.Suitable monomers comprises that those comprise the monomer of carboxyl, as acrylic acid, methacrylic acid or 2-acrylamido-2-methyl propane sulfonic acid, or preferred here these monomeric mixture.Preferably at least about 50 weight %, more preferably the described acid groups at least about 75 weight % is a carboxyl.Described acid groups is neutralized at least about 25mol%, the degree of preferred 25mol%～80mol%, and promptly described acid groups exists with the form of salt.Preferably obtain the polymer that the polymerization by acrylic or methacrylic acid obtains in the presence of internal crosslinker, the carboxyl of this polymer is neutralized to the degree of 50～80mol%.
The present invention relates to by the neutral super absorbent polymer of 2 footworks, the described undersaturated monomer that comprises acid groups that wherein will about 20mol%～about 75mol% neutralizes with first nertralizer, and the described undersaturated monomer that comprises acid groups that will about 5mol%～about 40mol% neutralizes with second nertralizer, so that total degree of neutralization is at least about the degree of 25mol%, preferred 50～80mol%.In the present invention, under about 75 ℃ or lower, preferred about 50 ℃ or lower temperature, neutralize.
Described first nertralizer is monovalence hydroxide, ammonia, carbonate, bicarbonate or other standard nertralizers as known in the art except multivalent metal hydroxides.Described first nertralizer also can be the mixture of mentioned reagent.Preferred monovalence metal hydroxides such as sodium hydroxide or potassium hydroxide and carbonate such as sodium carbonate or magnesium carbonate.Described second nertralizer is multivalent metal hydroxides such as calcium hydroxide and magnesium hydroxide.Described first nertralizer and second nertralizer can be joined in the described monomer solution continuously or simultaneously.Most preferably described first nertralizer is that sodium hydroxide and described second nertralizer are calcium hydroxide or magnesium hydroxide.Preferably realize at least 25%, more preferably at least 40% neutralization in addition by described first nertralizer.
Other monomers that can be used for preparing absorbable polymer according to the present invention be 0～40 weight % can with a) ethylenically unsaturated monomers of copolymerization, this monomer for example is (methyl) acrylate, dimethylaminopropyl acrylamide or the acrylamido oxypropyl trimethyl ammonium chloride of acrylamide, Methacrylamide, hydroxyethyl acrylate, (methyl) acrylic acid dimethylamino Arrcostab, ethoxylation.Can damage the swelling behavior of described polymer greater than these monomers of 40 weight %.
Described internal crosslinker have at least two ethylenic unsaturated double-bonds or ethylenic unsaturated double-bond and to the described polymerisable undersaturated monomeric acid groups that comprises acid groups be a reactive functional group or to can be used as described in linked and be present in the described polymerisable undersaturated monomer polymerization that comprises acid groups during the acid groups of component be reactive a plurality of functional group.
The example of internal crosslinker comprises aliphatic unsaturated amides, as methylene-bisacrylamide or di-2-ethylhexylphosphine oxide Methacrylamide or ethylenebis acrylamide; And the aliphatic (acid) ester of polyhydric alcohol or oxyalkylated polyhydric alcohol and ethylenic unsaturated acids, as two (methyl) acrylate or three (methyl) acrylate of butanediol or ethylene glycol, Polyethylene Glycol or trimethylolpropane; Two of trimethylolpropane preferably oxyalkylated, more preferably ethoxylation with 1～30mol alkylene oxide-and triacrylate; The acrylate of glycerol and tetramethylolmethane and methacrylate reach with the glycerol of the oxirane ethoxylation of preferred 1～30mol and the acrylate and the methacrylate of tetramethylolmethane; Allyl compound, as (methyl) allyl acrylate, with oxyalkylated (methyl) allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl maleate, poly allyl ester, tetraene propoxyl group ethane, triallylamine, the tetraallyl ethylenediamine of the reacting ethylene oxide of preferred 1～30mol; Glycol; Polyhydric alcohol; The allyl ester of hydroxyl pi-allyl or acrylate compounds and phosphoric acid or phosphorous acid; And other monomers that can be crosslinked, as the N-methylol compound of unsaturated amides (as Methacrylamide or acrylamide), and by its deutero-ether.Also can use ion crosslinking agent such as multivalent metal salt.Also can use the mixture of the described cross-linking agent of mentioning.Based on the described polymerisable undersaturated monomeric total amount that comprises acid groups, the content of described internal crosslinker is about 0.01～about 5 weight %, is preferably about 0.1～about 3.0 weight %.
To use always initiator be used to cause as azo or per-compound, redox system or UV initiator, (photosensitizer) and/or radiation as described in Raolical polymerizable.
Described absorbable polymer carries out surface-crosslinked after polymerization.Surface-crosslinked is any method of the crosslink density of the described polymeric matrix of the described superabsorbent particles near surface of raising for the crosslink density of described granule interior.Usually make that by adding surface crosslinking agent described absorbable polymer is surface-crosslinked.Preferred surface crosslinking agent comprises the chemicals with one or more functional groups, and described functional group is reactive to the side group of described polymer chain, and described side group typically is described acid groups.Based on the weight of described dry polymer, the content of described surface crosslinking agent is about 0.01～about 5 weight %, is preferably about 0.1～about 3.0 weight %.After adding described surface crosslinking agent, preferably carry out heating steps.
Normally, the present invention includes with alkylene carbonate and apply described graininess super absorbent polymer, surface-crosslinked by heating then to carry out, thus improve described surface-crosslinked density and gel strength characteristic.More specifically, by described polymer being mixed with the aqueous alcohol solutions of described alkylene carbonate surface crosslinking agent and surface crosslinking agent being coated on the described granule.The alcohol consumption is by the dissolubility decision of described alkylene carbonate and because of for example preventing that the technical reason that explodes from keeping low-level as much as possible with this consumption.Suitable alcohol is methanol, ethanol, butanols or butyl glycol and these pure mixture.Preferred solvent is a water, and with respect to the graininess super absorbent polymer, the typical amounts of water is 0.3～5.0 weight %.In some cases, described alkylene carbonate surface crosslinking agent is soluble in water under the condition that does not have any alcohol.Also can use for example be derived from inorganic carrier material (as SiO
2) the described alkylene carbonate surface crosslinking agent of mixture of powders, or use with gaseous state by the distillation of described alkylene carbonate.
In order to obtain desirable surface-crosslinked characteristic, described alkylene carbonate must be evenly distributed on the described graininess super absorbent polymer.For this reason, in suitable blender such as fluidized bed for solid mixing, blade-type mixer, roll or double-screw mixer, mix.Also can in a processing step during described graininess super absorbent polymer is produced, apply described specific super absorbent polymer.A kind of specially suitable method that is used for this purpose is the inverse suspension polymerization method.
Followingly after described coating processing, heat-treat.Normally, carry out described heat treatment in 100～300 ℃.Yet,, carry out described heat treatment in 150～250 ℃ if use described preferred alkylene carbonate.Described treatment temperature depends on the time of staying and the kind of alkylene carbonate.Under 150 ℃ temperature, described heat treatment was carried out 1 hour or longer.On the other hand, under 250 ℃ temperature, several minutes (for example 0.5～5 minute) is enough to fully obtain desirable surface-crosslinked characteristic.Can in traditional drying device, baking oven, fluidized bed dryer, double-screw reactor etc., carry out described heat treatment.
Though the example as the physical aspect of super absorbent polymer uses granule then, the present invention is not limited to this form, and applicable to other forms such as fiber, foam, film, pearl, club etc.
Based on the weight of described mixture, absorbable polymer according to the present invention can comprise the multivalent metal salt of 0～about 5 weight % on the surface of polymer.Described multivalent metal salt is preferably water miscible.The example of preferred metal cation comprises the cation of Al, Fe, Zr, Mg and Zn.Preferably, described metal cation has and is at least+3 quantivalence, wherein Al most preferably.The example of the preferred anionic in described multivalent metal salt comprises halide ion, chloride hydrate's ion, sulfate ion, nitrate ion and acetate ion, preferred chloride ion, sulfate ion, chloride hydrate's ion and acetate ion, more preferably chloride hydrate's ion and sulfate ion, most preferably sulfate ion.Aluminum sulfate be most preferred multivalent metal salt and easily commerce buy.The preferred configuration of aluminum sulfate is a hydrazine aluminum sulfate, preferably has the aluminum sulfate of 12～14 hydrate waters.Can use the mixture of multivalent metal salt.
Suitably by dry mixed or preferably in solution, use the mode that well known to a person skilled in the art that described polymer is mixed with multivalent metal salt.Preferred aqueous solutions.For dry mixed, adhesive consumption makes sufficient to guarantee keep the basic homogeneous mixture of described salt and described super absorbent polymer.Described binding agent can be at least 150 ℃ non-VOC for water or boiling point.The example of described binding agent comprises water, polyhydric alcohol such as propylene glycol, glycerol and poly-(ethylene glycol).
Absorbable polymer according to the present invention can comprise the water-insoluble inorganic powder that can reach about 0.01～about 5 weight %.The example of described insoluble inorganic powder comprises silicon dioxide, silicic acid, silicate, titanium dioxide, aluminium oxide, magnesium oxide, zinc oxide, Talcum, calcium phosphate, clay, kieselguhr, zeolite, bentonite, Kaolin, brucite, activated clay etc.Described insoluble inorganic powder additive can be for the unification compound or for being selected from the mixture of the above-mentioned chemical compound of enumerating.In all these examples, preferred trickle noncrystal silicon dioxide or aluminium oxide.In addition, the preferable particle size of described inorganic powder is 1,000 μ m or littler, more preferably 100 μ m or littler.
Super absorbent polymer according to the present invention can also comprise the surfactant that adds 0～about 5 weight % to described polymer beads surface.Preferably before the described surface-crosslinked step immediately, during or add described surfactant afterwards immediately.
The example of described surfactant comprises anion, nonionic, cation and amphoteric surfactant, as soap, coco amine and amide and salt, alkyl sulfate salt, alkylbenzenesulfonate, sulfo--dialkyl succinate, alkylphosphonate salt and laureth sulfate; Polyoxyethylene alkyl ether, polyoxyethylated alkyl phenol, polyoxyethylene fatty acid ester, sorbitan fatty ester, polyoxygenated sorbitan fatty ester, polyoxyethylene alkyl amine, fatty acid ester and epoxy ethane-epoxy propane block polymer; Alkylamine salt, quaternary ammonium salt; With the lauryl dimethyl amine oxide.Yet, and the described surfactant of nonessential qualification is above-mentioned those surfactants.Described surfactant can be used singly or in combination.
Described super absorbent polymer can also comprise the water-soluble polymer of 0～about 30 weight %, the for example polyvinyl acetate of partial hydrolysis or complete hydrolysis, polyvinylpyrrolidone, starch or starch derivatives, Polyethylene Glycol or polyacrylic acid are preferably polymerization in the form of (polymerized-in) wherein.The molecular weight of these polymer is also non-key, as long as they are water miscible.Preferred described water-soluble polymer is starch and polyvinyl alcohol.Based on component total amount a)～d), the preferred content of described water-soluble polymer in absorbable polymer according to the present invention is 0～30 weight %, is preferably 0～5 weight %.Described water-soluble polymer, preferred synthetic polymer such as polyvinyl alcohol also can serve as the grafting matrix that is used to treat polymerization single polymerization monomer.
Sometimes wish to use the surface additive of the multiple effect of performance during surface modification.For example, single additive can be surfactant, viscosity improver, and reacts so that polymer chain is crosslinked.
Described super absorbent polymer can also comprise the dedusting agent of 0～about 2.0 weight %, and for example hydrophilic and hydrophobic dedusting agent for example also can be with U.S. patent 6,090,875 and 5,994, and those that describe in 440 are used for method of the present invention.
Can choose other additives that use super absorbent polymer according to the present invention wantonly, as the abnormal smells from the patient bound substances, as cyclodextrin, zeolite, inorganic or organic salt and similar material; Agglomeration resistance additive, flow improving agent etc.
Preferably prepare polymer according to the present invention by two kinds of methods.Can pass through above-mentioned known method, prepare described polymer continuously or off and on, correspondingly carry out according to crosslinked after according to the present invention in large-scale industrial mode.
According to described first method, by in the presence of cross-linking agent and non-essential other components, in aqueous solution, carrying out radical polymerization the neutral monomer of described part, preferred acrylic acid are converted into gel, and with described gel pulverize, dry, the particle diameter that grinds and be sized to hope.This polymerisation in solution can be carried out continuously or off and on.
Also inverse suspension polymerization and emulsion polymerisation can be used to prepare article according to the invention.According to these methods, under the help of protecting colloid and/or emulsifying agent, monomer, the neutral aqueous solution of preferred acrylic acid part are dispersed in the hydrophobic organic solvent, and cause described polyreaction by radical initiator.Described internal crosslinker is dissolved in the described monomer solution and therewith is metered into, perhaps described internal crosslinker is added during described polyreaction individually and randomly.By described monomer solution or by being introduced directly in the oil phase, randomly add water-soluble polymer d) as described grafting matrix.Then water azeotropic from described mixture is shifted out, and leach described polymer and optionally drying.Can be by being dissolved in multifunctional cross-linking agent polymerization in the described monomer solution in wherein and/or by during polymerization procedure, the functional group reactions of suitable cross-linking agent and described polymer being carried out internal crosslinking.
In one embodiment, use described super absorbent polymer with the form of discrete particle.Described superabsorbent polymer particles can be any suitable shape, as spiral or semi-spiral, cube, bar-shaped, polyhedron etc.Here also can consider to use grain shape, as needle-like, lamellar or fiber with big greatest dimension/smallest dimension ratio.Also can use the aggregation of superabsorbent polymer particles.
Embodiment
Further explain the present invention by following embodiment, can not think by any way that described embodiment limits the scope of the present invention.On the contrary, can be expressly understood and have multiple other embodiments, modification and its equivalence, after the explanation of reading this paper, these other embodiments, conversion scheme and its equivalence are obvious to those skilled in the art under the situation that does not break away from spirit of the present invention and/or accessory claim.
Embodiment 1
Keeping below under 40 ℃ the temperature, will be neutralized to the degree of 60 moles of % with sodium hydroxide in constant cooling at the acrylic acid aqueous solution of 28 weight %, and with in the calcium hydroxide and other 10 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
Finish back (about 30 minutes) in described polyreaction, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Then, the solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 2
Keeping below under 40 ℃ the temperature, the acrylic acid aqueous solution of 28 weight % is neutralized to the degree of 50 moles of % with sodium hydroxide in constant cooling, and with in the calcium hydroxide and other 20 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Then, the solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 3
Keeping below under 40 ℃ the temperature, the acrylic acid aqueous solution of 28 weight % is neutralized to the degree of 30 moles of % with sodium hydroxide in constant cooling, and with in the calcium hydroxide and other 40 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
Finish back (about 30 minutes) in described polyreaction, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Then, the solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 4
Keeping below under 40 ℃ the temperature, the acrylic acid aqueous solution of 28 weight % is neutralized to the degree of 40 moles of % with sodium hydroxide in constant cooling, and with in the magnesium hydroxide and other 30 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Then, the solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 5
Keeping below under 40 ℃ the temperature, the acrylic acid aqueous solution of 28 weight % is neutralized to the degree of 30 moles of % with sodium hydroxide in constant cooling, and with in the calcium hydroxide and other 40 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Then, the solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
It is 150～300 microns that described granule is further sieved particle diameter.
Embodiment 6
Be lower than under 40 ℃ to keep temperature in constant cooling, the acrylic acid aqueous solution of 28 weight % be neutralized to the degree of 55 moles of % with sodium hydroxide, and with in the calcium hydroxide with other 15 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 7
Be lower than under 40 ℃ to keep temperature in constant cooling, the acrylic acid aqueous solution of 28 weight % be neutralized to the degree of 50 moles of % with sodium hydroxide, and with in the magnesium hydroxide with other 20 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Embodiment 8
Be lower than under 40 ℃ to keep temperature in constant cooling, the acrylic acid aqueous solution of 28 weight % be neutralized to the degree of 65 moles of % with sodium hydroxide, and with in the calcium hydroxide with other 5 moles of %.In the neutral acrylic acid solution of described part, add Polyethylene Glycol (300) diacrylate of 0.24 weight % and allyloxy Polyethylene Glycol-acrylate of 0.3 weight %.Be cooled to 5 ℃ and slough oxygen with nitrogen after, by adding 10ppm ascorbic acid, 100ppm 2,2 '-azo is two-(2-amidine propane) dihydrochloride, 70ppm hydrogen peroxide and 300ppm sodium peroxydisulfate, and make described mixture carry out polymerization with standard radical chain polymerization technology.
After described polyreaction (about 30 minutes) finishes, the gluey piece of gained is cut into small pieces and pushes by mould with 10mm hole.Then with described micelle in forcing air-oven in 150 ℃ dry 120 minutes down, after 30 minutes with respect to 180 ° of described polymer counter-rotating airflow direction.Described exsiccant polymer is ground and it is sieved particle diameter with the Retsch needle mill is 150～850 microns.
Solution with the 6.5 weight % that comprise 7.7 weight % ethylene carbonates, 30.8 weight % water and 61.5 weight % acetone evenly applies described base polymer.Then described coated polymer is heated to 180 ℃ and continues 25 minutes.
Table 1 has been summarized the material behavior of these materials and other super-absorbent materials.
Table 1
| The embodiment numbering | Balance FAUZL capacity (g/g) | Mean diameter (mm) | The 5+10a that calculates 2(minute) | The 7+10a that calculates 2(minute) | The 10+10a that calculates 2(minute) | The soak time of measuring (minute) | Drop osmotic value (second) | Gel bed permeability (* 10 -9cm 2) | 1/2 floating saturation (%) |
| 1 | 30.5 | 0.50 | 7.5 | 9.5 | 12.5 | 12.5 | ＜1 | 22 | 0 |
| 2 | 29.5 | 0.46 | 7.1 | 9.1 | 12.1 | 47 | ＜1 | 36 | 0 |
| 3 | 25.0 | 0.42 | 6.8 | 8.8 | 11.8 | 96.5 | ＜1 | 14 | 0 |
| 4 | 34.8 | 0.73 | 10.3 | 12.3 | 15.3 | 32.5 | ＜1 | 5 | 0 |
| 5 | 25.5 | 0.23 | 5.5 | 7.5 | 10.5 | 79.4 | ＜1 | - | 0 |
| 6 | 31.0 | 0.47 | 7.2 | 9.2 | 12.2 | 30 | ＜1 | 45 | 0 |
| 7 | 29.3 | 0.43 | 6.8 | 8.8 | 11.8 | 8 | ＜1 | 18 | 0 |
| 8 | 36.0 | 0.47 | 7.2 | 9.2 | 12.2 | 8 | ＜1 | 92 | 0 |
*Dry floating expression in above-mentioned table swims in salt particulate percentages waterborne when described superabsorbent particles is in dry not solvent swelling state.
Method of testing
Described method is used to carry out overflow absorbability (FAUZL) test under described salt water droplet penetration testing, described gel bed permeability (GBP) test, the test of described floatability, the test of described mean diameter and the described zero load.Except as otherwise noted, the described test fluid flow that uses in following all method of testings is 0.9 weight % sodium-chloride water solution, as obtaining from Ricca Chemical Company (Arlington, Texas).Except as otherwise noted, under about 70 degrees Fahrenheits and 10-60% relative humidity, carry out all tests.
Salt water droplet penetration testing
Design this test and drip the hydrophobicity of estimating SAP/ fine hair absorbent complex to use salt-water liquid.Described SAP/ fine hair ratio is 50/50, has the density of basic weight and the 0.2g/cc of 500gsm.By being cured, described sample quickened hydrophobicity formation in 120 minutes under 150 ℃ in hermetic container.Use pipet with every for 10 saline of about 0.05g are placed on the different parts of described sample, and measure every time of penetration that enters described sample.Measure every time of penetration independently.When drop touched described complex, every described time began.Independent time of penetration the longest in writing down 10 is as described drop time of penetration.
Under 150 ℃, cure and be equivalent in 120 minutes wear out at the laboratory of environmental condition down to the minority moon.Overflow absorption (FAUZL) under the zero load
Design the saline absorption rate that this test is used to measure graininess super absorbent polymer (SAP).This thermometrically is when it is limited to be in 5.07cm under definite nominal pressure of 0.01psi (0.069kPa)
2The salt water yield that the dry super absorbent polymer of 0.160g is absorbed in the time of in the area is as the function of time.From the Absorption of gained data, determine to reach the soak time of 60% described balance absorptive capacity to the time.
The electronic balance (minimum capacity of 200g) that is accurate to 0.001g is used in described test; The cylinder group, it comprises: 1 inch (25.4mm) internal diameter plastic cylinder 120 that is attached with 100 order stainless (steel) wires at the bottom of tube; With 4.4g plastic piston dish 122 with 0.995 inch (25.27mm) diameter.Described piston plate diameter is than described barrel bore little 0.005 inch (0.13mm).See Fig. 2.In addition, 0.9 weight % sodium-chloride water solution; Brine pit 126; Can read 120 minutes timer 140 with one second interval; With the pan paper (see figure 1).
As shown in Fig. 2 and 3, knocking device (tapping device) is placed on described sample top to provide stable knocking on described supporting piston dish.This knocks any entrapped air of having driven away around described superabsorbents, and the surface of guaranteeing the described super-absorbent material of liquid moistening.In this device, motor 128 is rotated axle, and this axle drives rod 130 along up-down stroke.As shown in FIG. 2, be that diameter is the rubber base plate 132 of 13mm in the lower end of described rod.Described axle stroke is 3cm, with and finished whole upper and lower stroke cycle in per 0.7 second.The maximum pressure that described piston plate is applied on the described SAP when impacting is 0.16psi (1.1kPa).
With reference to figure 1, fixture 134 has the find time vacuum ports 136 of interstitial liquid of permission from described sample.Described port can hold the substrate of described cylinder group.When the described cylinder group that will comprise described sample was placed on the described fixture, free fluid was removed between described superabsorbent particles.138 pairs of described samples of suitable pump apply-13.5psig (93.1kPa) or littler vacuum pressure.
Fig. 1 has shown described whole testing device.It should be noted that and suitably use electronic timer 140 to control the described persistent period of knocking with vacuum equipment.In this device, described knocking device also is placed in permission on the slideway 142 that moves between a plurality of samples.
Step
1. weighing 0.160g (± 0.001g) superabsorbents on the pan paper of pre-coating tar.Described particle size distribution is this super-absorbent material " former state obtains " particle size distribution.
2. described super-absorbent material is poured into lentamente in the described cylinder with 100 orders bottom.Because granule can adhere to, should avoid the granule of SAP to contact the side of described cylinder.Knocking described cylinder gently is distributed in described online up to the uniform particles of described SAP.
3. described plastic piston is placed in the described cylinder.This cylinder group of weighing also writes down described weight as " cylinder group super-absorbent material amount ".
4. fill the height of described salt basin with blood bank saline to 1cm.
5. described cylinder group is placed in the described salt basin, it just in time is lower than the axle of described knocking device and starts described timer.Start and operate described knocking device and reach circulation in 8 seconds to knock.
6. described cylinder being positioned in the described basin back 1 minute, shift out described cylinder, stop described timer, and described cylinder is put on the described vacuum platform, as shown in Figure 3.The vacuum that applies-13.5psig (93.1kPa) reached for 6 seconds.
7. the described cylinder group of weighing and write down described weight.
8. described cylinder group is turned back to and be lower than described knocking device in the described basin, and start described timer once more.Attention in step 6, from described saline, shift out described cylinder group to the time that in step 8, described cylinder group is caused the described saline more should be above 30 seconds.Repeat to soak, shift out, vacuum and the initial order of weighing to be to compile and record data when the accumulation soak time is 1,5,10,15,30,45,60,75,90 and 120 minute.
9. the method for describing in step 1～8 is implemented three times altogether.
Result and analysis
Calculate the saline gram number that every gram super absorbent polymer absorbs, and as the function construction of accumulating soak time.
Determine the final balance absorptive capacity of described SAP: if the variation of the average size of the described SAP that obtained (three times test meansigma methodss) less than 5%, then uses described capacity in the time of 120 minutes as balancing capacity FAUZL then in the time of 90 and 120 minutes.If there is the variation greater than 5% in described average size, then needs to repeat described sample test, and need be included in the additional sample of accumulation soak time when being 200 minutes.For this back kind situation, then use described capacity in the time of 200 minutes as balancing capacity FAUZL.
Determine to reach the interpolation time of 60% described balance absorptive capacity.This capacity of 60% o'clock by calculating described equilibrium valve, estimate that from described curve the corresponding time that reaches this capacity realizes then.Carry out the described interpolation time that linear interpolation obtains to reach 60% capacity (by this method) by using near the data point of the both sides of described estimated time.
Calculating reaches described arithmetic average interpolation time of 60% (meansigma methodss of three tests) of described balancing capacity.This meansigma methods is called " soak time ".
Gel bed permeability (GBP)
The suitable piston/cylinder device that is used for carrying out the GBP test is shown in Figure 4 and 5.With reference to figure 4, device 228 is made up of cylinder 234 and the piston that is generally denoted as 236.As shown in Figure 4, piston 236 is by having the cylindrical of concentric cylinder hole 240
Axle 238 is formed, and the longitudinal axis of described axle was bored in described hole 240 downwards.Machining was all carried out at the two ends of axle 238, to provide terminal 242 and 246.The counterweight that is denoted as 248 is placed on terminal 242, and has the cylindrical hole 248a that bored its center.Be inserted on the other end 246 is annular piston head 250.The size of design piston head 250 makes and vertically moves in cylinder 234.As shown in Figure 5, piston head 250 has the inside and outside concentric ring that comprises 7 and 14 about 0.375 inch (0.95cm) cylindrical hole respectively, represents with arrow 260 and 254 usually.Piston head 250 was bored in described hole in each concentric ring from top to down.Piston head 250 also has the heart therein and bored cylindrical hole 262 with the end 246 of accepting axle 238.
Be attached to cylinder 234 bottoms be before adhering to by biaxial stretch-formed to the No.400 order rustless steel cloth screen of tightening 266.Be attached to piston head 250 bottoms be before adhering to by biaxial stretch-formed to the No.400 order rustless steel cloth screen of tightening 264.To be denoted as 268 super-absorbent material sample support on net 266.
By transparent
Rod or equivalent Drilling cylinder 234, and internal diameter is 6.00cm (area=28.27cm
2), wall thickness is about 0.5cm and highly is about 5.0cm.Piston head 250 be from
Rod machining is come out.The height of this piston head be about 0.625 inch (1.59cm) and its diameter dimension of design make its in cylinder 234 with minimal wall clearance assembling but still can be free to slide.The opening (18 threaded line/inches) that has threaded 0.625 inch (1.59cm) that be used for axle 238 ends 246 in the hole 262 at described piston head 250 centers.The axle 238 be from
The rod mechanical machining external diameter that come out and that have 0.875 inch (2.22cm) and the external diameter of 0.250 inch (0.64cm).Terminal 146 be about 0.5 inch (1.27cm) long and by cutting thread with the hole 262 on the coupling piston head 250.End 242 is about 1 inch (2.54cm) length and diameter is 0.623 inch (1.58cm), forms the ring-type shaft shoulder to support rustless steel counterweight 248.The internal diameter of ring-type rustless steel counterweight 248 is 0.625 inch (1.59cm), so that it slides on axle 238 the end 242 and rests on the formed herein described ring-type shaft shoulder.The gross weight of piston 236 and counterweight 248 approximates 596g, and this is equivalent to be used for 28.27cm
2The 0.30psi of area (20.685 dyne/cm
2) pressure.
When flow of solution during through described piston/cylinder device, described cylinder 234 relies on 16 order rigidity rustless steel supporting network (not shown)s or the equivalent usually.
Place the sky cylinder to obtain size in described piston and counterweight from described counterweight bottom to described cylinder top.The slide calliper rule that use can be read 0.01mm obtain this size.To use this size to calculate the height of described gel bed later on.Measuring each empty cylinder and record, to have used which piston and counterweight be very important.When gel swelling, should use same piston and counterweight to be used for measuring.
By about 0.9g super-absorbent material is carried out the described superabsorbents layer that swelling was formed for the GBP measurement in about 60 minutes with 0.9 weight % sodium-chloride water solution in GBP cylinder unit (exsiccant polymer should be spread into equably the online of described cylinder before swelling).Described sample is taken from by U.S. standard #30 screen cloth and is sieved and be retained in super-absorbent material on the U.S. standard #50 screen cloth in advance.Therefore, the particle diameter of described super-absorbent material is 300～600 microns.Described granule can sieve by hand in advance, or with as available from W.S.Tyler, Inc., Mentor, the Ro-Tap formula moto-vibro screen Model B of Ohio carry out automatically pre-screening.
At the end of this period, from liquid, remove described cylinder and described piston counterweight assembly is placed on the described gel layer.By measuring the thickness of determining described swelling superabsorbents layer to the top of described cylinder from the bottom of described counterweight with micrometer.The value that obtains behind the described gel swelling deducts with empty cylinder carries out the described value that this measures.Income value is the height of described gel bed H.
By being joined, described NaCl solution when described solution has the height of the bottom 4.0cm that is higher than superabsorbents layer 268, starts described GBP measurement in the cylinder 234.In whole test, keep this solution height.The described amount of liquid that passes superabsorbents layer 268 along with the time is measured on gravimetric analysis ground.In two minutes of described test per 1 second ground and in all the other times per two seconds ground collect data point.When described data were mapped as the amount of liquid that passes described layer along with the time, it was tangible when obtaining to stablize flow velocity to those skilled in the art.Only will be used for described flow velocity calculating in case described flow velocity becomes the data of collecting when stablizing.By the liquid that passes described superabsorbents layer 268 (in the gram agent) is carried out linear least square fitting for the time (with second), determine described flow velocity Q in the described superabsorbents layer 268 of passing of gm/sec.
Obtain with cm by following equation
2The permeability of meter:
K＝[Q＊H＊Mu]/[A＊Rho＊P]
K=gel bed permeability (cm
2); Q=flow velocity (g/sec);
H=gel bed height (cm); Mu=liquid viscosity (pool);
A=is used for the area of section (cm of liquid flow
2); Rho=fluid density (g/cm
3); With P=hydrostatic pressure (dyne/cm
2) [be generally 3923 dyne/cm
2].
Floatability
Design the described floatability that this floatability test is used to measure graininess super absorbent polymer (SAP).
This test use 500ml beaker, two small cusp spatuves, tweezers, have plastic jar, saline, weigh scale and the timer of the about 2～3cm of internal diameter and highly about 3～4cm.
At first, spread over the SAP of 0.10g 300～600 μ m in the plastic jar and splash into saline (0.9%NaCl), make its presaturation level that reaches plan (as determined below here), cover described bottle then.Wait for equilibrium establishment (about 200 minutes).Then, use the small cusp spatula from described bottle, to take out SAP and be close to particulate substrate (particle by particle basis) and separate SAP by granule.About 300ml saline is put in the described beaker.From the height that is higher than the about 1cm of described salt water surface the SAP granule is dropped on the described brinish surface gently.When touching described salt water surface, described granule starts timer.Waited for for 45 seconds, and write down then described SAP granule be floating or the sinking.If sinking to be lower than described brinish surface then to think fully, all granules sink.Repeat test, up to 20 granules of test.Calculate the particulate percentage ratio of buoyant SAP.This equals " floating percent ".With the function construction of described floating percent as saturation.
The bottle that use has lid prepares described presaturation level." saturation " is defined as: saturation=be standardized to (liquid weight/dry SAP weight) in g/g of superabsorbents in the described balance FAUZL absorptive capacity (as defined above) of g/g.The SAP of weighing 0.1g.Described SAP is added drop-wise in the saline of desired amount, with obtain desirable saturated level (liquid/solid, g/g).Shake container and described saline is mixed to form homogeneous mixture as much as possible with described SAP.Described seal of vessel and wait are reached poised state (about 200 minutes).Then, begin described floatability test.
The mean diameter method of testing
Be positioned in the Ro-Tap formula moto-vibro screen with U.S. standard screen by sample and under qualifications, its vibration determined the particle size distribution of super-absorbent material stipulated time known weight.The sample that use is retained on each sieve tool partly calculates described mean diameter.
Take by weighing the superabsorbents of 25 ± 0.1g and keep and be used for test.Described screen cloth is laminated on the described Ro-Tap formula in the following sequence from bottom to top: chassis, 325 orders, 170 orders, 50 orders, 30 orders and 20 orders.The described superabsorbents sample that takes by weighing above to described top mesh (#20), is covered described screen cloth then.With described Ro-Tap formula running 10 minutes, stop then.Record is retained in the superabsorbents amount on each dish.The mass ratio that is retained in the superabsorbents on each screen cloth i is called m
i, and the ratio of the gross mass of reservation quality by measuring superabsorbents and superabsorbents is calculated described mass ratio.In order to calculate described mean diameter, suppose that all granules that keep on the specific screen have size r
i, this size equals the average of top screen cloth and described granule reservation screen cloth thereon.For example, deducibility is retained in superabsorbents on described 50 eye mesh screens and is 450 μ m (corresponding to 50 purposes, 300 μ m and average corresponding to 30 purposes, 600 μ m).Suppose that the sample that is retained on described 20 eye mesh screens is 1000 μ m sizes.Suppose that the sample that is retained on the described dish is 22 μ m (corresponding to 325 purposes, 44 μ m with corresponding to the average of 0 μ m of described dish).Therefore, the described mean diameter of following calculating:
Mean diameter=∑ m
i* r
i
The described embodiment that describes at inventive method has all demonstrated good overall performance, particularly the relation of reservation and Penetration Signature.Obtain the free-flow coating powders that can measure easily.
Claims (22)
1. hydrophilic superabsorbent polymer composition, it comprises the absorbable polymer as the product of following material:
A) the polymerisable undersaturated monomer that comprises acid groups of 55～99.9 weight %;
B) be selected from first nertralizer of monovalence hydroxide, monovalence carbonate or monovalence bicarbonate or its mixture;
C) comprise second nertralizer of multivalent metal hydroxides;
D) internal crosslinker of 0.001～5.0 weight %;
Wherein said absorbable polymer has the degree of neutralization greater than 20%, and under 75 ℃ or lower temperature, the described undersaturated monomer that comprises acid groups of 20mol%～75mol% is neutralized with first nertralizer, neutralize with second nertralizer with the described undersaturated monomer that comprises acid groups, and described absorbable polymer is shaped to granule 5mol%～40mol%; With
E) surface crosslinking agent that puts on the polymer beads surface of 0.001～5.0 weight %; With
The soak time of wherein said hydrophilic superabsorbent polymer composition is 5+10a
2Minute or longer, wherein a is the mean diameter of described super-absorbent material in millimeter, liquid capacity is 15g/g or bigger, the drop osmotic value is that 2 seconds or shorter and 1/2 floating saturation are 50% or littler.
2. the described superabsorbent polymer composition of claim 1, it has 20g/g or bigger liquid capacity.
3. the described superabsorbent polymer composition of claim 1, it has 25g/g or bigger liquid capacity.
4. the described superabsorbent polymer composition of claim 1, it has 7+10a
2Minute or longer soak time.
5. the described superabsorbent polymer composition of claim 1, it has 10+10a
2Minute or longer soak time.
6. the described superabsorbent polymer composition of claim 1, it has 20 * 10
-9Cm
2Or bigger gel bed permeability.
7. the described superabsorbent polymer composition of claim 1, it has 50 * 10
-9Cm
2Or bigger gel bed permeability.
8. the described superabsorbent polymer composition of claim 1, it has 80 * 10
-9Cm
2Or bigger gel bed permeability.
9. the described superabsorbent polymer composition of claim 1, wherein said first nertralizer is that the sodium hydroxide and second nertralizer are selected from calcium hydroxide or magnesium hydroxide.
10. the described superabsorbent polymer composition of claim 1 is wherein realized at least 40% neutralization by described first nertralizer.
11. the described superabsorbent polymer composition of claim 1, wherein said first nertralizer comprises the monovalence metal hydroxides.
12. it is water-fast, lightly crosslinked, part is neutral, hydrophilic superabsorbent polymer composition, it is based on the degree of neutralization of 20mol%～75mol%, wherein said hydrophilic super absorbent polymer is the polymerisable undersaturated monomer that comprises acid groups and is selected from monovalence hydroxide, monovalence carbonate, or bicarbonate, or the product of first nertralizer of its mixture, the described undersaturated monomer that comprises acid groups of 5mol%～40mol% is neutralized with second nertralizer that comprises multivalent metal hydroxides, and the soak time of wherein said hydrophilic superabsorbent polymer composition is 5+10a
2Minute or longer, wherein a is the mean diameter of described super-absorbent material in millimeter, liquid capacity is 15g/g or bigger, the drop osmotic value is that 2 seconds or shorter and 1/2 floating saturation are 50% or littler.
13. the described superabsorbent polymer composition of claim 12, it has 20g/g or bigger liquid capacity.
14. the described superabsorbent polymer composition of claim 12, it has 25g/g or bigger liquid capacity.
15. the described superabsorbent polymer composition of claim 12, it has 7+10a
2Minute or longer soak time.
16. the described superabsorbent polymer composition of claim 12, it has 10+10a
2Minute or longer soak time.
17. the described superabsorbent polymer composition of claim 12, it has 20 * 10
-9Cm
2Or bigger gel bed permeability.
18. the described superabsorbent polymer composition of claim 12, it has 50 * 10
-9Cm
2Or bigger gel bed permeability.
19. the described superabsorbent polymer composition of claim 12, it has 80 * 10
-9Cm
2Or bigger gel bed permeability.
20. hydrophilic superabsorbent polymer composition, it comprises the polymer as the product of following material:
A) the polymerisable undersaturated monomer that comprises acid groups of 55～99.9 weight %;
B) be selected from first nertralizer of monovalence hydroxide, monovalence carbonate or bicarbonate or its mixture;
C) comprise second nertralizer of multivalent metal hydroxides;
D) internal crosslinker of 0.001～5.0 weight %;
Wherein polymer has the degree of neutralization greater than 20%, and under 75 ℃ or lower temperature, the described undersaturated monomer that comprises acid groups of 20mol%～75mol% is neutralized with first nertralizer, neutralize with second nertralizer with the described undersaturated monomer that comprises acid groups, and resulting polymers is shaped to granule 5mol%～40mol%; With
E) surface crosslinking agent that puts on particle surface of 0.001～5.0 weight %.
21. the described superabsorbent polymer composition of claim 20 is wherein realized at least 40% neutralization by described first nertralizer.
22. the described superabsorbent polymer composition of claim 20, wherein said first nertralizer comprises sodium hydroxide and second nertralizer is selected from calcium hydroxide or magnesium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/660,982 | 2003-09-12 | ||
| US10/660,982 US7285614B2 (en) | 2003-09-12 | 2003-09-12 | Superabsorbent polymer with slow absorption times |
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| Publication Number | Publication Date |
|---|---|
| CN1878578A CN1878578A (en) | 2006-12-13 |
| CN100417422C true CN100417422C (en) | 2008-09-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800333606A Active CN100417422C (en) | 2003-09-12 | 2004-09-10 | Superabsorbent polymer with slow absorption times |
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| Country | Link |
|---|---|
| US (1) | US7285614B2 (en) |
| EP (1) | EP1675630B1 (en) |
| JP (1) | JP4810635B2 (en) |
| CN (1) | CN100417422C (en) |
| TW (1) | TWI318992B (en) |
| WO (1) | WO2005027987A1 (en) |
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| CA2608740C (en) * | 2005-05-16 | 2015-09-08 | The University Of Akron | Mechanically strong absorbent non-woven fibrous mats |
| BRPI0714447B1 (en) † | 2006-07-19 | 2019-02-19 | Basf Se | PROCESS FOR PREPARING WATER-ABSORBING POLYMERIC PARTICULATES, WATER-ABSORBING POLYMERIC PARTICULATES, USE OF POLYMERIC PARTICULARS, AND, HYGIENE ARTICLE |
| EP1886699B1 (en) * | 2006-08-07 | 2012-04-25 | The Procter & Gamble Company | Absorbent articles comprising superabsorbent polymers and a material with radiation-induced hydrophilicity |
| DE102006039205A1 (en) * | 2006-08-22 | 2008-03-20 | Stockhausen Gmbh | On renewable raw materials based acrylic acid and water-absorbing polymer structures and processes for their preparation by dehydration |
| DE102006060156A1 (en) * | 2006-12-18 | 2008-06-19 | Evonik Stockhausen Gmbh | Water-absorbing polymer structures produced using polymer dispersions |
| US8304369B2 (en) | 2010-05-07 | 2012-11-06 | Evonik Stockhausen, Llc | Superabsorbent polymer having a capacity increase |
| KR101477226B1 (en) * | 2011-08-11 | 2014-12-29 | 주식회사 엘지화학 | Monomer composition for preparing super absorbent polymer, its preparation method and preparation method of super absorbent polymer using the same |
| US8420567B1 (en) | 2011-12-30 | 2013-04-16 | Evonik Stockhausen, Llc | Process for superabsorbent polymer and crosslinker composition |
| JP2015503655A (en) | 2011-12-30 | 2015-02-02 | エボニック コーポレイションＥｖｏｎｉｋ Ｃｏｒｐｏｒａｔｉｏｎ | Superabsorbent polymer containing a cross-linking agent |
| US9302248B2 (en) | 2013-04-10 | 2016-04-05 | Evonik Corporation | Particulate superabsorbent polymer composition having improved stability |
| US9375507B2 (en) | 2013-04-10 | 2016-06-28 | Evonik Corporation | Particulate superabsorbent polymer composition having improved stability |
| JP5893116B2 (en) | 2014-07-11 | 2016-03-23 | 住友精化株式会社 | Water absorbent resin and method for producing water absorbent resin |
| CN109060580B (en) * | 2018-06-14 | 2020-12-15 | 超威电源集团有限公司 | Method for testing acid absorption saturation of storage battery separator |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4810635B2 (en) | 2011-11-09 |
| US20050059762A1 (en) | 2005-03-17 |
| WO2005027987A1 (en) | 2005-03-31 |
| EP1675630B1 (en) | 2016-03-09 |
| US7285614B2 (en) | 2007-10-23 |
| JP2007505193A (en) | 2007-03-08 |
| CN1878578A (en) | 2006-12-13 |
| TW200523307A (en) | 2005-07-16 |
| TWI318992B (en) | 2010-01-01 |
| EP1675630A1 (en) | 2006-07-05 |
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